Organic acid esters of 4-benzoyl-5-hydroxy(mercapto)pyrazoles

Abstract

An ester of a compound having the formula ##STR1## wherein R 1 represents hydrogen atom or a lower alkyl group, R 2 represents a lower alkyl group or a lower alkenyl group, n is an integer of 1 to 4, Z represents a halogen atom, nitro group, a lower alkyl group, a halogenated lower alkyl group, a lower alkoxy group, a lower alkanesulfonyl group, cyano group, a lower alkylthio group, an alkanoyl group having 2 to 5 carbon atoms, or benzoyl group, and when n is 2, 3, or 4, Z's may be the same or different. The esters are suitable for use in herbicidal compositions.

What is claimed is: 
     
       1. An ester of a compound having the formula ##STR14## wherein R 1  represents hydrogen atom or a lower alkyl group, R 2  represents a lower alkyl group or a lower alkenyl group,   n is an integer of 1 to 4,   Z represents a halogen atom, nitro group, a lower alkyl group, a halogenated lower alkyl group, a lower alkoxy group, a lower alkanesulfonyl group, cyano group, a lower alkylthio group, an alkanoyl group having 2-5 carbon atoms, or benzoyl group, and when n is 2, 3, or 4, Z's may be the same or different, and   Y represents oxygen atom or sulfur atom, with the proviso that when     Y is oxygen, and Z is a halogen, there must be 2, 3 or 4 such halogen substituents, and   Z is a lower alkyl, there must be 3 or 4 such lower alkyl substituents, and   Z is a lower alkoxy, there must be 3 or 4 such lower alkoxy substituents, and   Z is a cyano, there are 2, 3 or 4 cyano substituents; with an organic acid selected from the group consisting of: carboxylic acids having the formula     R.sub.3 COOH     wherein       R3 is an alkyl group having 1 to 17 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms and 1 to 4 halogen atoms,   an alkenyl group having 2 to 17 carbon atoms,   a 5-7 membered cycloalkyl group,   a phenyl group optionally having 1 to 3 substituents selected from the group consisting of nitro, a halogen, and   a C 1-4  alkyl,   a phenylalkyl group having 1 to 5 carbon atoms in the alkyl moiety and optionally having 1 to 3 substituents selected from the group consisting of nitro and a halogen in the phenyl moiety,   styryl group or   a phenoxyalkyl group having 1 to 3 carbon atoms in the alkyl moiety and optionally having 1 or 2 substituents selected from the group consisting of a halogen and methyl in the phenyl moiety; carbamic acids having the formula: ##STR15## wherein R 4  and R 5  each is an alkyl group having 1 to 4 carbon atoms or jointly form pentamethylene group; carbonic or thiocarbonic acid monoesters having the formula: ##STR16## wherein R 8  is an alkyl group having 1 to 4 carbon atoms, phenyl group or a phenylalkyl group having 1 or 2 carbon atoms in the alkyl moiety and optionally having 2 to 3 substituents selected from the group consisting of nitro and a halogen, and       Y is oxygen or sulfur atom; dibasic acids having the formula: ##STR17## wherein R 9  is an alkylene group having 1 to 10 carbon atoms, vinylene group or a phenylene group or both C═O groups may be linked without the R 9 , and     m is 0 or 1; and 3-oxo-4-isoxazolin-2-yl carboxylic acids having the formula: ##STR18## wherein R 10  is hydrogen atom or a halogen atom.     
     
     
       2. The ester of claim 1 wherein R 1  represents a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms,   R 2  represents an alkyl group having from 1 to 3 carbon atoms or an alkenyl group having 3 or 4 carbon atoms,   Z's are the same or different and each represents a halogen atom, an alkyl group having from 1 to 4 carbon atoms or a nitro group, and   n is an integer of 2 or 3.   
     
     
       3. The ester of claim 1 wherein R 1  represents a methyl group,   R 2  represents a methyl group or an allyl group,   Z's are the same or different and each represents a halogen atom, a methyl group, or a nitro group, and   n is an integer of 2 or 3.   
     
     
       4. The ester of claim 1 wherein R 1  represents a methyl group,   R 2  represents a methyl group,   Z's are the same or different and each represents a chlorine atom, a methyl group or a nitro group, and   n is an integer of 2.   
     
     
       5. The ester of claim 1 wherein R 1  represents methyl,   R 2  represents methyl,   n is an integer of 2 or 3, and   Z is methyl, nitro or halogen.   
     
     
       6. The ester of claim 1 wherein R 1  is hydrogen atom or an alkyl group having 1 to 6 carbon atoms,   R 2  is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 3 to 6 carbon atoms,   n is an integer of 1 to 3,   Z is a halogen atom, nitro group, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 or 2 carbon atoms and having 1 to 3 halogen atoms, an alkoxy group having 1 to 4 carbon atoms, an alkanesulfonyl group having 1 to 4 carbon atoms, cyano group, an alkylthio group having 1 to 4 carbon atoms, alkanoyl group having 2 to 5 carbon atoms, and when n is 2, or 3, Z's may be the same or different.     
     
     
       7. The ester of claim 1 wherein R 1  is hydrogen atom or an alkyl group having 1 to 3 carbon atoms,   R 2  is an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 3 to 4 carbon atoms,   Z is halogen atom, cyano group, nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkanesulfonyl group having 1 to 4 carbon atoms or trifluoromethyl group,   n is an integer of 1 to 3, and when   n is 2, or 3, Z's may be the same or different.   
     
     
       8. The ester of claim 1 wherein R 1  is methyl group,   R 2  is methyl group or allyl group,   Z is chlorine atom, nitro group, cyano group, methyl group, methoxy group, methanesulfonyl group or trifluoromethyl group and   n is an integer of 1 to 3, and when   n is 2 or 3, Z's may be the same or different.   
     
     
       9. The ester of claim 1 selected from the group consisting of 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-lauroyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-stearoyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-crotonyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzoyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-acetoxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-propionyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-isobutyryloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(5-methyl-3-oxo-4-isoxazolin-2-ylcarbonyloxy)pyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(3-oxo-4-chloro-methyl-4-isoxazolin-2-ylcarbonyloxy)pyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-methoxycarbonyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-n-propoxycarbonyloxypyrazole,   
     
     
       1. 3-dimethyl-4-(2,4-dichlorobenzoyl)-5-benzyloxycarbonyloxypyrazole, 1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenoxycarbonyloxypyazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-linoleyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-chloroacetoxypyrazole,   bis[1,3-dimethyl-4-(2-chloro-4-nitrobenzoyl)-5-pyrazolyl]succinate,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-pivaloyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenylthiocarbonyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-n-butylthiocarbonyloxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-phenylacetoxypyrazole,   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(2,4-dichlorophenoxyacetoxy)pyrazole   1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(2,4-dichlorobenzoyloxy)pyrazole,   1,3-dimethyl-4-(2,4-dichlorbenzoyl)-5-ethylthiocarbonyloxypyrazole,   1-allyl-3-methyl-4-(2,4-dichlorobenzoyl)-5-isobutyryloxypyrazole.